JPS63101472A - Solvent type treating agent for imparting water repellency and oil repellency and finishing method - Google Patents

Abstract

PURPOSE:To obtain a solvent type treating agent for imparting water repellency and oil repellency, which has excellent durability and feeling to touch, by blending a fluorinated water and oil repellant with a specified carboxy-modified diorgano-polysiloxane softener. CONSTITUTION:A treating agent consists of a fluorinated water and oil repellant (1) and a carboxy-modified diorgano-polysiloxane softener (2) having at least two -Q-COOR6 and being represented by the formula. In the formula, R1, R2, R3, R4 and R5 are each a 1-20C hydrocarbon group; R6 is H or a monovalent hydrocarbon group; A1 and A2 are each a 1-20C monovalent hydrocarbon group or -Q-COOR6 (wherein Q is a bivalent hydrocarbon group); m is an integer; n is 0 or >=1; m+n>=10; m/(n+2)=5/1-500/1. Examples of the fluorinated repellant are homopolymers of a vinyl monomer having a 4-18C fluoroalkyl or fluoroalkenyl group, copolymers of said monomers and copolymers of said monomer with a vinyl monomer contg. no fluorine.

Description

[Detailed description of the invention] [Object of the invention] (Industrial application field) The present invention imparts water and oil repellency to many base materials such as textile fabrics, carpets, raw cotton, paper, and plastics. This invention relates to a solvent-type water and oil repellent treatment agent.

More specifically, the present invention provides a solvent-based water and oil repellent treatment agent that is made of a fluorine-based water and oil repellent and a specific organopolysiloxane and imparts durable water and oil repellency to textile materials, and a method for processing the same. It is related to.

(Prior Art and its Problems) It has been well known that fluorine-based compounds exhibit excellent performance as water- and oil-repellent treatment agents for textiles and the like.

However, even though this excellent performance is washed and dry cleaned, the water and oil repellency apparently deteriorates significantly, and in order to regain this performance, conventional heat treatments such as ironing and heat pressing have been used. It was essential.

This is due to shedding of the fluorine-based water and oil repellent treatment agent or structural problems, and in order to fully develop water and oil repellency, an arrangement of fluoroalkyl groups or fluoroalkenyl groups is required. This is presumed to be because of this, but for consumers who actually use water- and oil-repellent textiles, ironing them after washing is a hassle, even if the dry cleaning itself can be outsourced to a professional. Moreover, ironing is not an easy task when it comes to items with complex shapes, and there are some items that are not normally ironed, such as diaper covers. The emergence of a drug was awaited.

In order to meet these demands, a method using a polyisocyanate compound (Japanese Patent Application Laid-open No. 165072/1982) and a method using a blocked isocyanate compound (Japanese Patent Application Laid-open No. 165072/1989) were proposed.
No. 0-151378) and the like have been proposed, but they are not necessarily satisfactory and have the disadvantage that the texture becomes rougher and stiffer.

(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present inventors have discovered that various base materials, typically textile materials, have particularly good recovery of water and oil repellency after washing, and that As a result of intensive research to develop a solvent-based water and oil repellent treatment agent that does not require any heat treatment such as cliffing or heat pressing, we have developed a product that uses a combination of a fluorine-based water and oil repellent agent and a specific organopolysiloxane type softener. The present inventors have discovered that the treatment agent exhibits excellent properties such as durability and texture, and have completed the present invention.

[Structure of the invention]

(Means for Solving the Problems) To summarize the present invention, the first invention consists of (g) a fluorine-based water and oil repellent; The present invention relates to a solvent-type water and oil repellent treatment agent comprising: a carboxy-modified diorganopolysiloxane softener having at least two carboxy-modified diorganopolysiloxane molecules in the molecule;

Further, a second invention relates to a water- and oil-repellent processing method, characterized in that a workpiece is processed with the solvent-type water- and oil-repellent processing agent according to the first invention.

Hereinafter, the configuration of the present invention will be explained in detail.

The above-mentioned fluorine-based water and oil repellent, which is an essential component of the water and oil repellent treatment agent in the present invention, is a vinyl monomer having a 04 to C18 fluoroalkyl group or a fluoroalkenyl group, or These are copolymers or copolymers of these and vinyl monomers that do not contain fluorine. Typical examples of the vinyl monomers having a fluoroalkyl group or fluoroalkenyl group include the following: It will be done.

CyF15CH20COCH=CHz, Cl0F190
CH2CH20COCH-CHz, 08F17CH2C
H20COCH=CHz, C3F17SO2N (C3H
y) CH2CH20COCH-CHz, C3F17SO
2N(CH2)CH2CH20COC(CHa)=CH
z On the other hand, typical examples of the fluorine-free vinyl monomer include ethylene, propylene, butylene, butadiene,
Isoprene, chloroprene, vinyl chloride, nylidene chloride, styrene, ester or amide of (meth)acrylic acid and alcohol or alkylamine (all C20 or less), diacetone acrylamide, N-methylolacrylamide, acrylonitrile, acrylamide, vinyl acetate , vinyl compounds with siloxane bonds, etc. Two or more of these monomers can also be used in combination.

These homopolymers or copolymers can be obtained by solution polymerization using a radical initiator by a known method for vinyl polymerization. The molecular weight of the polymer can be adjusted to a preferable range depending on the concentration of the initiator and the type and concentration of the chain transfer agent, but generally from the viewpoint of developing water repellency, it is
,000 or more is preferable.

As the carboxy-modified diorganopolysiloxane softener, which is another essential component of the water- and oil-repellent treatment agent of the present invention, those represented by the general formula (I) as described above are used. In the general formula (I), R1 to R5 have 1 to 1 carbon atoms;
20 monovalent hydrocarbon groups, including methyl group, ethyl group, propyl group, pentyl group, dodecyl group, stearyl group, 3
, 3.3-trifluoropropyl group, β-phenylethyl group, α-methyl-β-phenylethyl group, and phenyl group. Methyl groups are most common as R1-R5, but combinations of methyl groups and other groups are also common. R6 is a hydrogen atom or a monovalent hydrocarbon group, and examples of the latter include a methyl group, an ethyl group, and a hexyl group. AI, A2 is R1-R5 or 10-COOR6, and A1. When both A2 are the latter, the general formula (D
It is also possible for n to be O. The general formula (
In I), m+n is at least 10 because 10
This is because if it is less than this, the effect of imparting flexibility and smoothness to fiber fabrics etc. will be poor. Also m/(n+2)=5
/1 to 500/1 because if it is less than 5/1, the effect of imparting flexibility and smoothness will be poor, and if it exceeds 500/1, the effect of imparting compression recovery property and elongation recovery property will be poor. be.

Both of the above components include, for example, toluene, xylene, benzene,
Prepare a treatment bath by dissolving it in an organic solvent such as n-hexane, pbutane, mineral turpentine, perchloroethylene, 1.1.1-trichloroethane, etc., and apply it to textile fabrics, etc. by spraying, dipping, kiss roll, etc. Is possible.

The usage ratio of fluorine-based water and oil repellent and carboxy-modified diorganopolysiloxane-based softener is based on the solid content (non-volatile content).
The former/latter is 20/1 to 1/20, preferably 5
/1 to 1/10. If the usage ratio is more than 20/1, the durability and flexibility imparting effect of the water and oil repellent properties to fiber fabrics etc. will be poor, and if it is less than 1/20, the water and oil repellency will decrease from the early stage of processing. It comes out.

The substrates to which the solvent-based water and oil repellent treatment agent of the present invention thus obtained can be applied include commonly used textile materials, as well as paper, wood, leather, fur,
There is a wide range of products including plastic products (films, sheets, molded products), painted surfaces and plasters.

Typical textile materials mentioned here include cotton,
Natural fibers such as linen, wool or silk; synthetic fibers such as polyamide, polyester, polyurethane, polyvinyl alcohol, polyacrylonitrile or polyvinyl chloride; or semi-synthetic fibers such as rayon or acetate. Of course, it can also be used for fiber fabric materials that are a mixture of these materials, and also for products such as carpets, raw yarn, raw cotton, etc.

(Examples) Next, the present invention will be described in more detail based on Examples, but the present invention is not limited only to these Examples. Water repellency, oil repellency, and texture shown in the following examples were evaluated using the following scale. In other words, the water repellency is JIS
It is expressed by water repellency Nα (see Table 1 below) determined by L-1092 spray method, and oil repellency is expressed by AATCC-118.
It was expressed by oil repellency Nα (see Table 2 below) determined by the hydrocarbon resistance method. Furthermore, the texture was evaluated based on the tactile sensation according to the evaluation criteria shown in Table 3.

Synthesis Example 1 CgF17SO2N (C3H7)CH2CH20CO
C= CH280g, stearyl acrylate 20g,
150 g of 1,1.1-trichloroethane, 0.13 g of n-dodecyl mercaptan, and 0.5 g of azobisisobutyronitrile were placed in a four-bottle flask with a capacity of 3007, and after being sufficiently purged with nitrogen, A polymerization reaction was carried out at C for 12 hours.

After the reaction was completed, the polymer concentration was measured and found to be 39.8%.

Furthermore, the fluorine-containing polymer solution (
Synthesis Example 1) was prepared.

Synthesis example 2 CgF17S02N (CaH7) CII2CHzOCO
A fluorine-containing polymer solution (Synthesis Example 2) was prepared in the same manner as Synthesis Example 1 except that CaF1yCIIzCHzOCOC=Ctl 2 was used for H3 instead of CH=CH2.

Synthesis example 3 CgF17012CHzOCOC1l =CH260f
f Benzyl methacrylate 30 g Dioctyl maleate 103 was dissolved in 150 g of 1.1.1-trichloroethane, and a polymerization reaction was carried out in the same manner as in Synthesis Example 1. This solution was diluted with 1.1.1-trichloroethane and adjusted to a polymer concentration of 15%, which was used as a fluorine-containing polymer solution (Synthesis Example 3).

Synthesis example 4 C[13 08F17CH2CH20COC= CM 2
70'; J stearyl acrylate 209t
-Butyl methacrylate 5g was dissolved in 150g of 1.1.1-trichloroethane, polymerized in the same manner as in Synthesis Example 1, and further diluted with 1,1°1-trichloroethane to adjust the polymer concentration to 15%. A fluoropolymer solution (Synthesis Example 4) was prepared.

<Examples 1 to 5> To 3 parts of the fluorine-containing polymer solution of Synthesis Example 1, a carboxy group-containing diorganopolysiloxane represented by the formula and having a viscosity of 2500 centistokes and 1.1.
1-trichloroethane was added in the proportions shown in Table 4 to make a total of 100 parts to prepare a uniform treatment solution. After immersing the nylon tack and polyester taffeta in this treatment solution, they are pulled up and wet picked up with a mangle roll.
It was narrowed down to 0%. Then, it was pre-dried at 100'C for 2 minutes and heat-treated at 170'C for 30 seconds. Initial processing and JIS L-0217/103
Table 4 shows the water-repellency and oil-repellency of the samples that were washed 20 times using the same method and dried at room temperature for 24 hours.

Comparative Example 1 A treatment liquid was prepared in the same manner as in Example 1 except that the compound crab was not used, and it was applied to a fiber fabric. Initial machining and 2
Table 4 shows the water and oil repellency after 0 washes.

Comparative Examples 2 to 5 Treatment liquids were prepared in the same manner as in Example 1, except that Compounds A to D shown below were used in place of Compound (1), in the proportions shown in Table 4, and applied to fiber fabrics. Initial machining and 2
Table 4 shows the water and oil repellency after 0 washes.

An epoxy group-containing diorganopolysiloxane represented by Compound A and having a viscosity of 8000 centistokes.

An epoxy group-containing diorganopolysiloxane having a viscosity of aooo centistokes.

Compound C: An amino group-containing diorganopolysiloxane having a viscosity of 1 ioo centistokes.

A diorganopolysiloxane containing carbinol groups and having a viscosity of 170 centistokes.

Examples 6 to 10 and Comparative Examples 6 to 8 Fluorine-containing polymer solutions (synthesis examples 1 to 4) as shown in Table 5
) and the above compound (1) and the following compounds (2) to (3) were adhered to nylon taffeta (wet pick-up 20%) and polyester processed yarn fabric (wet pick-up 70%) in the same manner as in Example 1. Table 5 shows the results. Also shown.

However, compounds ■ and ■ are as follows.

A carboxy-modified diorganopolysiloxane having a viscosity of 200 centistokes expressed in the Kakura Hikidara formula.

Compound (1) A carboxyl group-containing diorganopolysiloxane represented by the formula and having a viscosity of 2550 centistokes.

As shown in Tables 4 and 5, the treated fabric treated with the solvent-based water and oil repellent treatment agent of the present invention exhibits a soft texture and excellent recovery of raw water and oil repellency after washing. ing.

Margins below [Effects of the Invention] The solvent-based water and oil repellent treatment agent of the present invention can be applied to various base materials, but when applied to textile fabrics, for example, after washing, there is almost no heat treatment and only air drying is required. It is possible to restore the original water and oil repellency and provide a soft texture.

Although it is unclear why the present invention sufficiently restores water and oil repellency after washing, it is possible that the flexibility and smoothness of the fluorine-based water and oil repellent due to friction during washing can be improved. It is inferred that one of the reasons is that only the dropout and the orientation of the perfluoroalkyl group are reduced.

Claims (1)

[Claims] 1. (1) Fluorine-based water and oil repellent; (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) In the formula, R_1, R_2, R_3, R_4, R_5 are A monovalent hydrocarbon group having 1 to 20 carbon atoms, R_6 is a hydrogen atom or a monovalent hydrocarbon group, A_1 and A_2 are 1 having 1 to 20 carbon atoms
valence hydrocarbon group or -Q-COOR_6, where Q is 2
valence hydrocarbon group, m is a positive integer, n is an integer of 0 or 1 or more, m + n is at least 10 or more, m / (n + 2) = 5
/1 to 500/1. A solvent-type water and oil repellent treatment agent comprising a carboxy-modified diorganopolysiloxane softener represented by the following formula and having at least two -Q-COOR_6 groups in one molecule. 2. (1) Fluorine-based water and oil repellent and (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) In the formula, R_1, R_2, R_3, R_4, R_5 are carbon atoms of 1 to 20. Monovalent hydrocarbon group, R_6 is a hydrogen atom or monovalent hydrocarbon group, A_1 and A_2 are 1 having 1 to 20 carbon atoms.
valence hydrocarbon group or -Q-COOR_6, where Q is 2
valence hydrocarbon group, m is a positive integer, n is an integer of 0 or 1 or more, m + n is at least 10 or more, m / (n + 2) = 5
/1 to 500/1. A solvent-based water- and oil-repellent finishing method characterized by using together a carboxy-modified diorganopolysiloxane softener represented by the following formula and having at least two -Q-COOR_6 groups in one molecule.